Hydrocyanation of olefins

ABSTRACT

A PROCESS FOR HYDROCYANATING AN ETHYLENICALLY UNSATURATED ORGANIC COMPOUND IN THE PRESENCE OF A ZERO VALENT NICKEL COMPLEX OF THE FORMULA NI(PXYZ)3R2CN AND NI(PXYZ)2A, WHEREIN X IS OR, Y AND Z ARE R OR OR AND R IS AN ALKYL OR ARYL RADICAL, A GIVEN PXYZ LIGAND HAVING A CONE ANGLE WITH AN AVERAGE VALUE BETWEEN 130* AND 170*; &#34;A&#34; IS AN ETHYLENICALLY UNSATURATED ORGANIC COMPOUND CONTAINING 2 TO 20 CARBON ATOMS; R2 IS AN ALKYL, ALKENYL, CYANO SUBSTITUTED ALKYL, OR ARYL GROUP HAVING 1 TO 20 CARBON ATOMS. A LEWIS ACID SUCH AS ALCL3, ZNCL2 OR (C6H5)3B MAY BE USED IN CONJUNCTION WITH THE COMPLEX.

United States Patent O 3,798,256 HYDROCYANATION F OLEFINS Charles Morgan King, William Carl Seidel, and Chadwick Alma Tolman, Wilmington, Del., assignors to E. I. du Pont de Nemours and Company, Wilmington, Del. No Drawing. Filed Aug. 2, 1971, Ser. No. 168,352 Int. Cl. C07c 121/04 US. Cl. 260465.8 R 11 Claims ABSTRACT OF THE DISCLOSURE A process for hydrocyanating an ethylenically unsaturated organic compound in the presence of a zero valent nickel complex of the formulae Ni(PXYZ) R CN and Ni(PXYZ) A, wherein X is OR, Y and Z are R or OR and R is an alkyl or aryl radical, a given PXYZ ligand having a cone angle with an average value between 130 and 170; A is an ethylenically unsaturated organic compound containing 2 to 20 carbon atoms; R is, an alkyl, alkenyl, cyano substituted alkyl, or aryl group having 1 to 20 carbon atoms.

A Lewis acid such as AlCl ZnCl or (C H B may be used in conjunction with the complex.

BACKGROUND OF THE INVENTION It is known that the addition of hydrogen cyanide to double bonds adjacent to an activating group such as a nitrile or a carboxy group proceeds with relative ease. However, the addition of hydrogen cyanide to non-activated double bonds proceeds only with difiiculty if at all and normally requires the use of high pressure of about 1,000 p.s.i. or more and high temperatures in the range of 200 to 400 C.

In US. Pat. 2,571,099 an improvement over this technique is described which involves the use of nickel carbonyl with or without the addition of a tertiary aryl phosphine or arsine. Relatively poor yields are obtained with this process along with the production of a relatively high percentage of undesirable polymeric products. More recently processes for elfecting hydrocyanation under mild conditions with tetrakis zero valent nickel complexes derived from phosphorus containing ligands have been described in US. Pats. 3,496,215, 3,496,217 and 3,496,- 218. Still further improvement in methods for hydrocyanation is desired particularly in respect to the development of systems providing high rate of reaction SUMMARY OF THE INVENTION The present invention provides a process which produces nitriles or dinitriles in high yields under mild conditions by reaction of olefins with hydrogen cyanide in the presence of zero valent nickel complexes with two or three esters of trivalent phosphorus along with an olefin or a nitrile.

The process of the present invention is generally applicable to unsaturated organic compounds containing from 2 to 20 carbon atoms having at least one ethylenic carbon-carbon double bond. The unsaturated organic compounds are of the class consisting of aliphatic and aromatic hydrocarbons and aliphatic and aromatic hydrocarbons containing functional groups consisting of and --NR wherein R" is hydrogen or an alkyl or aryl radical having from 1 to 10 carbon atoms and each open bond is connected to hydrogen or an aliphatic or aromatic hydrocarbon radical, wherein the carbon-carbon double bond is insulated from the aforesaid group by at least 1 carbon atom. 1

Patented Mar. 19, 1974 Suitable unsaturated compounds include monoolefins such as ethylene, propylene, butene-l, pentene-Z, hexene- 2, etc., substituted olefins such as B-pentenenitrile, 4-pentenenitrile, 2-methyl-3-butene nitrile, styrene or methylstyrene, as well as other unsaturated compounds shown in the examples.

The desired nickel compounds are nickel complexes of the formulae Ni(PXYZ) R CN and Ni ('PXY Z) A wherein X is OR, Y and Z are R or OR and R is an alkyl or aryl radical having up to 18 carbon atoms and the groups are so chosen that the ligand has a cone angle with an average value between and 170; wherein A is an unsaturated organic compound containing from 2 to 20 carbon atoms and having at least one olefinic carboncarbon double bond of the class consisting of aliphatic and aromatic hydrocarbons and aliphatic and aromatic hydrofcarbons substituted with functional groups consistmg 0 the case of ethylene [bis(tri-o-tolylphosphite)] nickel (0) whose use is illustrated in Examples 12-13, or they can be prepared in situ as is illustrated in Examples 1 to 11 wherein the coordinatively unsaturated zero valent nickel complex Ni[P (O-o-C H CH ,1, serves as the precursor for the active catalyst species. The complexes can also be prepared in situ by reduction of a divalent nickel compound with a metal more electropositive than nickel. The reduction can be carried out in a saturated aliphatic dinitrile solvent such as adiponitrile or 2-methylglutaronitrile along with an appropriate triaryl phosphite ligand. Useful nickel compounds include halide salts such as nickel chloride, nickel bromide or nickel iodide as well as nickel salts of carboxylic acids, sulfonic acids or sulfuric acid. Suitable reducing metals, that is, metals more electropositive than nickel in the saturated aliphatic dinitrile solvent, include Na, Li, Mg, Ca, Ba, Sr, Ti, V, Fe, Co, Cu, Zn, Cd, Al, Ga, In Sn Pb and Th.

The complexes can also be prepared by treating an organonickel compound with a suitable ligand. The particular species present during hydrocyanation will depend on specific reaction conditions concentration of reactants, etc. In the course of a typical hydrocyanation it is considered that the species Ni(PXYZ) A or Ni(PXYZ) R CN or both will be present; X, Y, Z, A and R being defined as above; the amounts will depend on the particular complex employed, the solvent if used, for example, acetonitrile and the extent of hydrocyanation.

The R groups in a given trivalent phosphorus ester ligand PXZY may be cojoined and may be the same or different and are so chosen as stated above that the ligand has a cone angle with average value between 130 and 170, preferably between and The cone angle is determined as described by C. A. Tolman, J. Am. Chem. Soc. 92-2956 (1970). The aryl groups may be substituted with alkyl, halogen or other groups provided the groups do not interfere with the catalyst function. Mixed ligands can be used. Typical trivalent phosphorus ester ligands include tri-o-tolyl phosphite (cone angle 141), phenyl di-o-tolyl phosphonite (cone angle 142) and tri-(2,5-xylyl) phosphite (con angle 144).

The organic nitriles represented by R CN include lower alkyl nitriles such as acetonitrile, propionitrile or butyronitrile which may be employed as solvents in the hydrocyanation as well as unsaturated nitriles such as 3-pentenenitrile or 4-pentenenitrile and products of the reaction of hydrogen cyanide with the unsaturated compounds mentioned above and shown in the examples such as adiponitrile.

A promoter may be used to improve the activity of the catalyst for the hydrocyanation reaction and to control distribution of the products. The promoter generally is a cationic form of the metal selected from the class of zinc, cadmium, beryllium, aluminum, gallium, indium, thallium, titanium, zirconium, hafnium, erbium, germanium, tin, vanadium, niobium, scandium, chromium, molybdenum, tungsten, manganese, rhenium, palladium, thorium, iron and cobalt. Among these the cations of zinc, cadmium, titanium, tin, chromium, iron and cobalt are preferred. Suitable promoters of this type are salts of the metals listed above and include aluminum chloride, zinc chloride, cadmium iodide, titanium trichloride, titanium tetrachloride, zinc acetate, ethyl aluminum dichloride, chromic chloride, stanous chloride, zinc iodide, nickel chloride, cerous chloride, cobaltous iodide, cadmium chloride, molybdenum dichloride, Zirconium chloride, thorium chloride, ferrous chloride and cobaltous chloride. The anion portion of the compound may be a halide such as fluoride, chloride, bromide and iodide, anions of lower fatty acids of from 2 to 7 carbon atoms, HPO3=, H2PO2 CF3COO C7H15OSO2 S04: etc.

Also useful as a promoter in the hydrocyanation reaction described above are the borohydrides and organo boron compounds of the formulae B(R and B(OR wherein R is of the class consisting of hydrogen, aryl radicals of from 6 to 18 carbon atoms, aryl radicals substituted with groups that do not interfere, lower alkyl radicals of from 1 to 7 carbon atoms and lower alkyl radicals of from 1 to 7 carbon atoms substituted with a cyano radical. Generally, the case where R is phenyl or phenyl substituted with an electronegative radical is preferred, as in the structure wherein Q is of the class consisting of H, F and CF;;.

The preferred borohydrides are the alkali metal borohydrides and the quaternary ammonium borohydrides particularly the tetra (lower alkyl) ammonium borohydrides and borohydrides of the formula B H where n is an integer of from 2 to 10, and B H where m is an integer of from 4 to 10. 'Of these, sodium borohydride and potassium borohydride are especially preferred.

The promoter acts to improve catalyst life (moles of product/mole of nickel complex) and, in certain cases, the yield and rate. This is particularly evident in the hydrocyanation of 3- or 4-pentenenitrile to adiponitrile. The amount of promoter used generally can be varied from about 1:16 to 50:1 molar ratio of promoter to catalyst. The promoter may be used according to several techniques. Thus, while at least some of the promoter may be added to the reaction mixture at the start of the reaction, additional amounts may be added at any point in time during the reaction.

It is believed that the organoboron compounds of the present invention have three levels of activity as follows. First, the principal most active promoter which is believed m have the formula B(R wherein R has the meaning defined above. Second, intermediate boron hydrides of the formula B H or B H which, it is believed, reacts with the olefin being hydrocyanated to form an organo boron compound of the formula )3 wherein R is derived from the olefin. For example, when B H is the boron hydride and 3-pentenenitrile is the olefin the principal promoter is believed to be and other isomers. Third, an alkali metal borohydride or quaternary ammonium borohydride which when used as the promoter is believed to form an intermediate borohydride B H or B H l in the reaction mixture which, in turn, forms a borane B(R which becomes the principal promoter.

The hydrocyanation reaction can be carried out by charging a reactor with all of the reactants or the reactor is charged with a catalyst or catalyst components, the unsaturated organic compound, the promoter and whatever solvent is to be used and hydrogen cyanide gas is swept over the surface of the reaction mixture or bubbled through the reaction mixture. Alternately, the hydrogen cyanide may be introduced in liquid form or in the form of the corresponding cyanohydrin. If desired, when using a gaseous unsaturated organic compound, the hydrogen cyanide and the unsaturated organic compound may be fed together into the reaction medium. Another technique is to charge the reactor with a catalyst, promoter, hydrogen cyanide and solvent to be used and thereafter feed the unsaturated compound slowly to the reaction mixture. The molar ratio of unsaturated compound to catalyst generally is varied from about 10:1 to 200011 unsaturated compound to catalyst for a batch operation. In a continuous operation such as when using a fixed bed catalyst type of operation, a much higher proportion of catalyst may be used, such as 122 unsaturated compound to eatalyst. The reaction medium is generally agitated such as by stirring or shaking.

In some instances it may be desirable to use an excess of the ligand (PXYZ) when carrying out the hydrocyanation reaction. The excess ligand may be added to the reactor along with the pre-formed complex, or in the case of in situ preparation of the complex an excess of the ligand may be introduced from which the complex will then be formed.

The hydrocyanated product can be recovered by conventional techniques such as by distillation or by crystallization of the product from solution.

The hydrocyanation reaction can be carried out with or without a solvent. The solvent should be liquid at the reaction temperature and inert toward the unsaturated compound and the catalyst. Generally such solvents are hydrocarbons such as benzene or xylene or nitriles such as acetonitrile or benzonitrile.

The exact temperature which is prefered is dependent to a certain extent on the particular catalyst being used, the particular unsaturated compound being reacted and the desired rate. Generally temperatures of 50 C. to 150 C. can be used. The reaction can be carried out at pressures from about 0.05 to about atmospheres. The nickel complexes of this invention permit hydrocyanation at high rates with low by-product formation.

The nitriles formed by the present invention are useful as chemical intermediates. For instance, adiponitrile is an intermediate used in the production of hexarnethylene diamine, which in turn is used in the production of polyhexamethylene adipamide, a commercial polyamide useful in forming fibers, films and molded articles. Other nitriles can be used to form the corresponding acids and amines which are conventional commercial products.

PREFERRED EMBODIMENTS In the preferred embodiments of this invention the hydrocyanation is carried out at a temperature in the range of about 15 C. to about 75 C. and at a pressure in the range of about 0.05 to about 10' atmospheres.

The preferred nickel complexes are those wherein the R groups of the phosphite ester ligands are ortho tolyl.

The preferred promoters are cations of zinc, aluminum, cadmium, titanium, tin, chromium,'iron and cobalt and boron compounds such as"ti'iphenyl' berm. v

The invention is further illustrated in the exam'pIe's to follow. Examples 1 to 11 illustrate in situ preparation of the complex'by addition of Ni[P(O-o-C H4CH to the reactor, where the zero valent nickel complex described above is rapidly-transformed to species repre- S6I1t6d Ni[P(OO'C6H4CH3)3]2[A], and

Ni,[P o-o-c. .cH3)2]3[R CN 1,

A and R being defined as in the preceding description.

EXAMPLE 1 A 50 ml. three necked, round bottom glass flask fitted with a reflux condenser connected to a Dry Ice trap, a gas inlet above liquid level and a magnetic stirrer was set up in an oil bath at about 70 C. The flask was purged with dry, deoxygenated nitrogen and charged with 2.0

H C H NCHzCH=0 H2 EXAMPLES 2-11 The hydrocyanations in these examples (Table I) were carried out following the procedure described in Example 1. For Examples 8-10 a reaction flask of 100 ml. volume was used. In Example 3 toluene in the amount of 80 ml. was added as solvent. The designations used in the Table refer to the following: ADN, adiponitrile, Z-MGN, 2.- methylglutaronitrile, ESN, ethylsuccinonitrile.

TABLE I Tem- HON perarate, Time, ture, Example Olefin Catalyst precursor I a Promoter m1./hr. hrs. 0. Product 2 -Ni[P(O-0 -CoH4CHa)a]a (2- grams) ZI1C12 (0.5 g.)...- 0. 6 21 25 Show nitrile; IR

' band at 2,240 CHzOH 01117 3 O 0.4 20 70 Do.

0 10 g. 4 Co;Is]g1CHzCH=CH: .d0 B(CaH5)' (1.0 g.) 0. 6 20, 5 Do, 5 p fin 1.0 20 70 Do.

. /CCaHs 6 Y H '-.---d0'- 511012 (0.6 g.) 1. 1 20 D0.

26 m1. 7 ..do 00012 (0.25 g.). 0.6 21 90 Do.

)o-o-oH;

8. B-pentenenitrlle, 20 ml.. N u 5)( 0C1 4CHa)2]a ZnClz (0.5 g.) 0. 5 17 25 Conversion 0.58%; '(0.75.grams). i g0gikgN, 40% 9 3-pentenenitrile, 25ml": Niu 0elH;0Ha l1; 1.0 00012 0.4 g.) 0.5 17 120 Conversion 6.1%; g a i 54% ADN, 38%

, v 2-MGN, 7% 'ESN. 10 3-pentenemtnle, 25 m1 T1013 (0.33 g.) 0.5 17 100 Conversion-5.2%; 49% ADN, 39%

. V 2-MGN 10% ESN. 11 3-pentenenitn'1e, 26 m a-m-N l -0Ca 40Ha)ah (1.25 A101, 0.3 5 75 ADN 279%;

' MGN1.5%;

ESN0.37%.

*Prepared as described by-L. .Gos s er and Tolma'n, "IndrganicGhemistryf 9-2350 (1970). 7

EXAMPLES 12-13 'Hydrocyanation of 3-pentenenitrile The hydrocyanations summarized in Examples 12-13 (Table II) were carried out following substantially the procedure of Example 1. The olefin charged for hydrocyanation was 3-pentenenitrile in the amount of 26 ml. The catalyst complex used in each case was 1.0 g. of ethylene[bis(tri -o:-tolyl phosphite)] nickel (0), made as de- TABLE II Product, percent Promototer ADN 2 MGN ESN Example:

12 ZnCh (0.85 g.) 4. 88 3. 56 0.47 13 1. as 1.50 0. 6g

ADN adiponitrile; 2 MGN, Z-methylglutaronitrile; ESN, ethylsuccinomtrile.

EXAMPLE 14 Preparation of complex by reduction of nickel compound with an active metal A glass reactor fitted with a stirrer, a nitrogen inlet and outlet and a fritted glass bottom was purged with nitrogen, then charged with 5.18 g. of nickel chloride, 2.87

g. of zinc dust, 60 ml. of adiponitrile and 60 m1. of triorthotolyl phosphite. The mixture was maintained at 100 C. with an infrared lamp and stirred for 1.25 hours. The resulting red liquid was filtered by vacuum through the fritted bottom of the reactor. The filtrate was sparged with anhydrous ammonia for one hour, during which the temperature which was initially at 25 C. was brought briefly to 100 C., then filtered to yield 81.35 g. of redbrown complex solution, believed to comprise predominantly Ni [P (O-o-C H CH 3 NC (CH CN.

EXAMPLE 15 Hydrocyanation of B-pentenenitrile with ZnCl promoter and excess ligand The reaction was carried out in a 100 ml. glass flask fitted with a nitrogen inlet for initial purge, a mechanical stirrer, a thermocouple and a syringe pump for liquid feed. The flask was sparged with nitrogen, then charged with 20 ml. of 3-pentenenitrile, 4 ml. of catalyst solution prepared as in Example 14, 4 ml. of tri-orthotolyl phosphite, and 0.8 ml. of a 33% by weight solution of ZnCl in 3-pentenenitrile. The reaction mixture was cooled to 6 C. and with stirring, a 1:1 mole mixture of S-pentenenitrilezI-ICN was fed by syringe pump at a rate of 0.3 ml. per minute for 3 hours and 25 minutes. The injection of about 1 ml. of 4-pentenenitrile showed a marked increase in rate of reaction as shown by temperature increase. The total reaction product weighed 67.33 g. Gas chromatographic analysis showed that the crude product contained 55.6% dinitriles of which 81.4% was adiponitrile.

EXAMPLE 16 Hydrocyanation of 3-pentenenitrile with tripheny boron promoter and excess ligand The reaction was carried out by the procedure described in Example 15 by charging the reactor with 20 ml. of 3-pentenenitrile, 4 ml. of complex solution as described in Example 14, 4 ml. of tri-orthotolyl phosphite and ml. of a solution of triphenyl borane containing 5 g. of

B(C H in 50 ml. of 3-pentenenitrile. The reaction mix- Total weight of crude product was 53 g. Gas chromatographic analysis showed that the crude product con- 8 tained 43.43% dinitriles of which 90.9% was adiponitrile, 8.5% was 2-methylglutaronitrile and 0.6% was ethyl succinonitrile.

EXAMPLE 17 Hydrocyanation of 3-pentenenitrile with Cr(adiponitrile) Cl promoter The Cr(adiponitrile) Cl promoter was prepared by heating a mixture of 121.5 g. of CrCl '6H O, 782 g. of 3-pentenenitrile, 125 ml. of adiponitrile and about 0.1 g. of zinc dust in a glass still at 70 mm. pressure to remove by distillation a total of 170 ml. of distillate of which 46 ml. was water. Fifty milliliters of the pot residue was removed and 5 ml. of 2,4-pentanedione was added to the remaining pot residue. The mixture was refluxed for one hour, then cooled and used as a promoter in the following hydrocyanation.

The hydrocyanation reaction was carried out by the procedure described in Example 15 by charging the reactor with 20 ml. of 3-pentenenitrile, 4 ml. of complex solution as described in Example 14 and 4 ml. of a solution of Cr(adip0nitrile) Cl prepared as shown above. The reaction mixture was maintained at 27 C. and with stirring a 1:1 mole mixture of 3-pentenenitrilezHCN was fed by syringe pump at a rate of 0.4 ml. per hour for 14.5 hours. Total weight of the crude product was 53.1 g. Gas chromatographic analysis showed that the crude product contained 45.2% dinitriles of which 84.6% was adiponitrile.

EXAMPLE 18 Hydrocyanation of 3-pentenenitrile with TiCl promoter and excess ligand The reactor for preparing the complex described in Example 14 was charged with 5.18 g. of NiCl 2.87 g. of zinc dust, 60 ml. of tri-orthotolyl phosphite, and 60 ml. of 2methylglutaronitrile. The mixture was maintained at C. with an infrared lamp and stirred for 1.25 hours. Two teaspoons of air-free filter-aid were added and the'mixture was filtered by vacuum through the fritted bottom of the reactor. Two teaspoons of filter-aid were added to the filtrate, the mixture was returnedto the reactor, heated to 100 C. and sparged with anhydrous ammonia for 20 minutes. The mixture was then filtered through the reactor frit; the filtrate was distilled at 0.5 mm. pressure until the pot temperature reached C. removing about 45, ml. of 2-methylglutaronitrile. The pot residue was extracted with 400 ml. of dry heptane; the red heptane layer was separated and the heptane removed by vacuum leaving the complex as the residue. Elemental analysis showed the product to contain 1.009% nickel and 0.128% zinc.

A hydrocyanation reactor as described in Example 15 was charged with 25 ml. of 3-pentenenitrile, 0.3 g. of TiCl 4 ml. of the complex described above and 2 ml. of triorthotolyl phosphite. The reaction mixture was maintained at about 27 C. and with stirring a 1:1 mole mixture of 3-pentenenitrilezHCN was fed by syringe pump at a rate of 0.15 ml. per hour for 2 hours and 10 minutes. The total reaction product weighed 44.0 g. Gas chromatographic analysis showed that the crude product contained 31.5% dinitriles of which 83.1% was adiponitrile.

EXAMPLES 19-23 (tri-o-tolyl phosphite)] nickel (0); for Examples 20 and 21 tris(tri-o-tolyl phosphite) nickel (0); for Examples 22 was added with ethylene gas spargirig-to removeoxygfqn.

9 10 and 23 ethylene[bis(tri-2,5-xylyl,phosphite)]nickel What .isclaimedis: The latter complex was made'as follows. v y A. process of hydrocyanating an unsaturated re To 3 molesof 2,5-xylenol hf'ld. t.a"emperatur of act ant organic [compound of the class consisting of 3- abou t-70' C. there was added. onefmol' pen 'tenenitrile: and 4-pentenenitrile trichlorideover aperiod of two';hou The whic lncomprises reacting said unsaturated organic comture was heated at reflux overnight iinderf nitrp "nspa'rge' enna with hydrogen cyanide in the presence of a after which the product, tri-2,5,-xylyl phos U tilled at 235 C. (0.25 mm).

, iivas disnickelcomplex of the class consisting of 2 In a one-liter 3-neck flask fitted with aDean- St I V p v NKPXYZ) 3R CN 3. mixture of 20.0 g. of nickel acetyl cjetonat'e, m rid Ni'(PXYZ)M; [Ni(acac) (H O) and 300 ml. of tol en waslheated at wherein X is OR, Y and Z are R or OR and R is an reflux to remove 1.3 ml. or water. jtjh ieactioni ixture if, a ky o a yl radical having p to 18 carbon atoms; was cooled to0 C. and 50 ml. of tri:-2,5,-xyl phosphite wherein the R radicals of a given PXY Z ligand may be 4 ined, may be the same or dilferent and are so Following this 104 ml. of a 25% solution ot] triethyl chosen that the ligand has a cone angle with an average aluminum in hexane wasadded with stirring over min yaluef between 130 and 170; utes. The mixture was warmed'to room temperature and rcui A is an unsaturated organic compound of the after one-half hour was again cooled to 0C. and thereass consisting of monoolefinic hydrocarbons and ole after methanol was carefully added-at a rate of :1 m1. /5 7 C l yd containing functional groups minutes for one-half hour following which slow methanol 20 1 selected from the class consisting of addition was continued until,gas evolution ceased and a total of 600 ml. of methanol had been added. The reaction mixture was cooled to C. and held at that temperature overnight, then transferred to a dry box and filtered. Recrystallization from a minimum of hot (60 C. toluene 25 solution, filtering through a medium glass frit and prelie'rein'R' is selected from the class consisting of hyg n and alkyl and aryl radicals having up to 10 arbonatoms and any open bond other that that recipitating with an equal volumeot methanol gave a yelquiredtor-"connection of the functional group to the low solid (60% yield). olefinic radical is connected to a radical of the class Calculated for C H NiO P C, 68. 9; H, 6.2;; Ni, 6.7, consisting of hydrogen and aliphatic and aromatic hy- P, 7.1. Found: C, 68.3; H, 6.6; Ni, 6.6; P, 6.9. dro carbon radicals, wherein the carbon-carbon bond TABLE III Product, percent Tem r- Example Ligand Promoter Nickelcomplex ature, C. ADN' MGN ESN' oTTP- 3.0m1.) A101: (0.1 g.) NiLzCzHt' (0.4 25 --do NaBHi (0.1 NlLi (1.0g.)- 25 d0 B(OCIH5)I( .5 g.) 0 50 2,5121": 3.0 m1.). ZnCh (0.1 g.) NlLgCzHa (0.4 22

I Orthotrltolyl phosphite.

b 2,5-xyly1 phosphite.

' Adiponitrlle.

d B-methylglutarorfltrlle.

' Ethylsuccinonitrile.

! L=tri-o-tolyl phosphite.

I L=tri-2,5-xylyl phosphite;

EXAMPLES 24-26 is separated from the aforesaid group by at least one Hydrocyanation of 3-pentenenitrile in the presence of a P nickel complex prepared in situ by ligand substitution or R2 15 of the class conslstmg 9 alkyl, FY by reduction of a nickel compound is illustrated in these saluted alkyl, alkenyl and y Iadlcals havmg 1 t0 20 examples. In all cases 20 ml. of 3-pentenenitrile was incarbon M01118, wherein e ca bon-carbon double bond troduced into the reactor after the complex was prepared. of the alkenyl radical is sepal'ated from the nitfile Hydrogen cyanide was then fed at a rate of 0.1 ml. per group y at least one carbon a hour for 16 hours. The results are summarized in Table at a temperat e in the range of t0 IV. and at a pressure in the range of about 0.05 to about EXAMPLE 27 100 atmospheres, the molar ratio of the unsaturated compound to the nickel complex being from 1:2 to Hydrocyanation of 3-pentenen1tr1le 1n the presence of a nickel complex prepared in situ by reduction of a nickel 1 and recgvermg the hydrocyanated reactant compound is further illustrated in this example. g fi 12 3;2 laim 1 wherein PXYZ i orthotri The nickel complex was prepared by reacting 2.63 g. p s

of M101 1.33 g. of zinc dust, 198.1 ml. of 3-pentenenif ff f 1 1 h th t trile and g. of tri-o-tolyl pbosphite under nitrogen prpcess calm w Crew 0 e emperature o maintained m the range of about 15 C. to about 75 sparge at q two hours Ten grams of thls C. and the hydrogen cyanide is supplied to the reaction 39 product to whlch a further 9 s'pentenem' medium by bubbling it through the reaction medium or 1 e was added, was reacted at 60 C. with 12.3 ml. of Sweeping it over the Surface of the reaction mixture hydrogenpyamde over a planed of 20 hours to gwc 65 4 The rocess of claim 2 wherein there is resent g. of hqurd product, of which 1.056% was ethylsuccinop p in addition to the nickel complex as a promoter a cation was methylglutarommle and 3,5314% was of a metal selected from the group consisting of zinc,

TABLE IV Product, percent Tempera- Time, ture h Example Nickel source Reducing agent Solvent 1'. ADN e MGN ESN- 24 (Qyclooctadiene)zNi (0.3 g.)-... O'ITP (3.0 ml.) 50 C 1 5. 38 1. 08 0. 1 25 N Ch (0.5 g.) Cd (dust; (0.5 g.) CH;CN (15 OT'IP (4 ml.) Reflux.-.. 4 1.92 .28 26 NlClr (0.1 g.) Zn (dust (0.1 g.) CHaCN (10 m1. OTTP (2 ml.) ......d0.... 4 3.29 .93 0.1

See footnotes a, c, d, and e at and of Table III.

cadmium, beryllium, aluminum, galliumpindium, thallium, titanium, zirconium, hafnium, erbium, germanium, tin, vanadium, niobium, sc'andium, chromium, molybdenum, tungsten, manganese, rhenum, thorium, iron, and cobalt, the mole ratio or promoter to nickel complex being in the range of about 1:16 to 50:1.

5. The process of claim 4 wherein the promoter is a cation of a metal selected from the group consisting of zinc, aluminum, cadmium, titanium, tin,. chromium, iron and cobalt. v I h 6. The process of claim 5 wherein the anion portion of the compound containing the metal cation is "o'i the class consisting of fluoride, chloride, bromide, iodide, anions of lower fatty acids of from 2 to 7 carbon atoms, HPO3=, H2POz CqHmOSOg' 804 7. The process of claim 2 wherein there is present, in addition to the nickel complex as a promoter a boron compound of the class consisting of alkali metal and tetra (lower alkyl) ammonium borohydrides, borohydrides of the structure B H wherein n is an integer of from 2 to 10 and B H wherein m is an integer of from 4 to 10 and organo boron compounds of the formulae B(R and B(OR wherein R is of the class consisting of aryl radicals of from 6 to 18 carbon atoms, lower alkyl radicals and cyano substituted lower alkyfradicals, the mole ratio of promoter to nickel complex being in the range of about 1:16 to 50:1. I

8. The process of claim 7 wherein the organic boron compound is triphenyl borane.

9. The process of claim 1 wherein the nickel complex is formed in situ by feeding into a reactor a saturated aliphatic dinitrile of vthe class consisting of adiponitrle and Z-methylglutaronitrile, a divalent nickel compound, a finely-divided'reducing metal of the class consisting of zinc and cadmium and a PXYZ ligand, X, Y and Z being defined as in claim 1. p

' 10. The process of claim 1 wherein the nickel complex is formed by feeding to a reactor an organonickel compound with a PXYZ ligand, X, Y and Z being defined asin claim 1.

' lL The process of claim 2 wherein A is an unsaturated organic compound of the class consisting of 3- pent'euenitrile 'and 4-pentenenitrile'and R is of the class consisting of Z-butenyl, 3-butenyl and cyano substituted alkyl radicals.

.. References Cited iUNITED STATES PATENTS 3,496,210 2/1970' Drinkard, Jr. et al.

' 260-4653 X 3,496,215 2/1970 Drinkard et al. 260-465.8 3,496,217 2/19'70 Drinkard, Jr. et al. 260--465.8 -3,496,218 2/1970 Drinkard, Jr. 260465.8

JOSEPH BRUST, Primary Examiner US. Cl. X.R.

vie-10w UNITED STATES PATENT omen CERTIFICATE OF CORRECTION Pat nt N 3 72 3% Dated Marchl9, 1974 Inventofls) Charles Morgan King, William Carl Seidel, and

Chadwick Alma. Tolman It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as ahown below:

- Column 10, line 26, the word "that", first occurrence, should read than--; line 60, the claim reference number "1" should read --2-- Signed and sealed this 1st day of October 1974.

(SEAL) Attest: V

MCCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents 

